This invention relates to an xcex1-amino-N-allylamidino nitrobenzene compound and process for its preparation.
The photographic art employs couplers to provide colored dyes in image reproductions. The couplers react imagewise with color developer to produce the desire reproduction. One of the couplers useful for this purpose is a pyrazolo[1,5-b][1,2,4]triazole compound that has found utility for forming a magenta dye in the usual system employing subtractive primaries.
Such couplers and methods of making them were originally disclosed in U.S. Pat. No. 4,621,046. Other methods have been disclosed in U.S. Pat. Nos. 4,705,863 and 6,020,498. The latter patent suggests the use of certain N-alkylamidino nitrobenzene derivatives for synthesizing intermediates in the process. It is desirable, however to provide alternative processes for preparing the desired compounds, especially processes that can provide improved yields.
The invention provides a process comprising reacting an N-allylimino nitrobenzene compound with a diaminodinucleophile to form an xcex1-amino-N-allylamidino nitrobenzene compound and also provides the compound itself as a composition of matter.
The invention provides a useful process for synthesizing useful compounds employing allyl groups. Embodiments of the invention can provide improved yields compared to prior art processes.
The invention is summarized above. The process of the invention is generally shown in reaction scheme 3 in the following scheme. 
In reaction 3, an N-allylimino nitrobenzene compound is reacted with a diaminodinucleophile to form an xcex1-amino-N-allylamidino nitrobenzene compound. Suitably, the reaction is carried out in the presence of a solvent that is inert under the reaction conditions. Useful solvents may be selected from the group consisting of C1 to C8 aliphatic alcohols, chlorinated or unchlorinated aromatic hydrocarbons such as toluene, the xylenes, monochlorobenzene or dichlorobenzenes, chlorinated or unchlorinated aliphatic hydrocarbons, ethers such as tetrahydrofuran, and esters such as ethyl acetate or isopropyl acetate. Preference is given to using alcohols, in particular isopropyl alcohol. In particular the reaction may be carried out using a mixture of toluene and isopropyl alcohol where the 3-tert-butyl-5-aminopyrazole in an isopropyl alcohol solution is added to a toluene solution of the amidine.
The reaction is exothermic and conveniently carried out at a temperature ranging from xe2x88x9210xc2x0 C. to +30xc2x0 C. and desirably from 0 to 15xc2x0 C.
The reaction is carried out with the diaminodinucleophile being present in stoichiometric quantity or in excess compared to the xcex1-amino-N-allylamidino nitrobenzene compound, with an excess of up to 0.5 mols/mol and a range of 1 to 1.25 mols/mol preferred. The compound is one having at least two nucleophilic nitrogen atoms and may include a ring compound such as an 3-tert-butyl-5-aminopyrazole.
Reaction 3 is typically described using the above captioned equation and the following limitations:
Z and X may independently be halogen, alkoxy, aryloxy, alkylthio, arylthio or heterocyclic groups;
R1, R2, and R3 may independently be hydrogen, halogen, alkoxy, aryloxy, alkylthio, arylthio, (cyclo-)alkyl, alkenyl, alkynyl, silyl or heterocyclic groups; provided that R1, R2, and R3 may also be contained within a carbocyclic or heterocyclic aromatic or non-aromatic ring system;
R4 and R5 may independently be hydrogen, halogen, alkoxy, aryloxy, alkylthio, arylthio, alkyl, alkenyl, alkynyl, silyl or heterocyclic groups; provided that R4 and R5 may also be contained within a carbocyclic or heterocyclic aromatic or non-aromatic ring system; and
Y is a leaving group such as hydroxy, halogen, alkoxy, aryloxy, acetoxy, siloxy, mesylate or tosylate. The preferred leaving groups are mesylate or tosylate.
The reaction may be represented by the following reaction 3 
wherein
Z and X are independently selected from halogen, alkoxy, aryloxy, alklthio, arylthio and heterocyclic akyl groups and n is 0 to 4;
R1, R2, R3 are independently selected from H, halogen, alkoxy, aryloxy, alkylthio, arylthio, alkyl, saturated or unsaturated cyclohydrocarbyl, heterocylic, aroyl, alkenyl, alkynyl, and silyl groups, provided that R1, R2, R3 may also be contained within a ring system; and
R4 and R5 are independently selected from H, halogen alkoxy, aryloxy, alkylthio, arylthio, alkyl, saturated or unsaturated cyclohydrocarbyl, hetereocylic, aromatic, aryl, alkenyl, alkynyl, silyl, provided that R4 and R5 may also be contained within a ring system.
The starting amide can be prepared using known methods, for example where the amine can be reacted with an acyl halide, an anhydride, an ester, or direct coupling with a carboxylic acid. (Woodcock, D. J. in Patai The Chemistry of the Amino Group; Wiley: N.Y., 1968, p. 440.)
In order to carry out step 2, use is generally made of a chlorinating agent such as, in particular, thionyl chloride (SOCl2), phosphorus pentachloride (PCl5), phosphorus oxychloride (POCl3), phosgene (COCl2), or oxalyl chloride (COCl)2, or one of their mixtures as more fully described in:
SOCl2 Lawson, A.; Miles, D. H. ; J Chem Soc [JCSOA9] 1959, 2865.
POCL3 Harris, R. L. N.; Synthesis [SYNTBF] 1980 (10), 841.
PCl5 Madronero, R.; Vega, S.; Synthesis [SYNTBF] 1987 (7), 628.
(COCl)2 Fujisawa, T.; Mori, T.; Sato, T.; Tetrahedron Lett [TELEAY] 1982, 23 (48), 5059.
Preference is given to using thionyl chloride. The chlorinating agent is employed in stoichiometric quantity or in excess. For reasons of economy, the quantity of chlorinating agent is preferably from 1 to 1.25 mol per mol of amide. The reaction can be carried out without solvent, with the chlorinating agent then serving as the solvent, or in the presence of a solvent or a mixture of solvents which are inert under the reaction conditions and which are selected from chlorinated or unchlorinated aromatic hydrocarbons such as toluene, the xylenes, monochlorobenzene or the dichlorobenzenes, or chlorinated or unchlorinated aliphatic hydrocarbons such as ethane or dichloromethane. Toluene is very suitable.
The temperature of this reaction is generally between 25xc2x0 C. and the reflux temperature of the solvent. When toluene is the chosen solvent and the chlorinating agent is thionyl chloride, the temperature is, in particular, between 70xc2x0 C. and 110xc2x0 C.
Catalysts such as N,N-dialkylated amides, in particular dialkylated formamides whose alkyl groups possess from 1 to 8 carbon atoms, such as N,N-dimethylformamide and, more especially, N,N-dibutylformamimde, can be added in order to accelerate the reaction. In general, the chlorination lasts between 2 and 15 hours. Once the reaction has finished, it is not necessary to isolate the chloroimine that is formed from the reaction medium.
General conditions for forming the oxime are described in the following literature:
C. G. McCarty, xe2x80x9cChemistry of the Carbon-Nitrogen Double Bondxe2x80x9d Ed. S. Patai, Interscience, New York (1970), pp 408-439;
J. A. Gautier, M. Miocque and C. C. Farnoux, xe2x80x9cThe Chemistry of Amidines and Imidatesxe2x80x9d, Ed. S. Patai, Interscience, New York, (1975) pp 313-314.
Steps 5 and 6 are ring closure reactions and are more fully described in U.S. Pat. No. 4,705,863.
Unless otherwise specifically stated, use of the term xe2x80x9cgroupxe2x80x9d, xe2x80x9csubstitutedxe2x80x9d or xe2x80x9csubstituentxe2x80x9d means any group or radical other than hydrogen. Additionally, when reference is made in this application to a compound or group that contains a substitutable hydrogen, it is also intended to encompass not only the unsubstituted form, but also its form further substituted with any substituent group or groups as herein mentioned, so long as the substituent does not destroy properties necessary for the intended utility. Suitably, a substituent group may be halogen or may be bonded to the remainder of the molcule by an atom of carbon, silicon, oxygen, nitrogen, phosphorous, or sulfur. The substituent may be, for example, halogen, such as chloro, bromo or fluoro; nitro; hydroxyl; cyano; carboxyl; or groups which may be further substituted, such as alkyl, including straight or branched chain or cyclic alkyl, such as methyl, trifluoromethyl, ethyl, t-butyl, 3-(2,4-di-t-pentylphenoxy) propyl, cyclohexyl, and tetradecyl; alkenyl, such as ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, 2-methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 2-(2,4-di-t-pentylphenoxy)ethoxy, and 2-dodecyloxyethoxy; aryl such as phenyl, 4-t-butylphenyl, 2,4,6-trimethylphenyl, naphthyl; aryloxy, such as phenoxy, 2-methylphenoxy, alpha- or beta-naphthyloxy, and 4-tolyloxy; carbonamido, such as acetamido, benzamido, butyramido, tetradecanamido, alpha-(2,4-di-t-pentyl-phenoxy)acetamido, alpha-(2,4-di-t-pentylphenoxy)butyramido, alpha-(3-pentadecylphenoxy)-hexanamido, alpha-(4-hydroxy-3-t-butylphenoxy)-tetradecanamido, 2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolin-1-yl, N-methyltetradecanamido, N-succinimido, N-phthalimido, 2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, and N-acetyl-N-dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino, 2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino, 2,5-(di-t-pentylphenyl)carbonylamino, p-dodecyl-phenylcarbonylamino, p-tolylcarbonylamino, N-methylureido, N,N-dimethylureido, N-methyl-N-dodecylureido, N-hexadecylureido, N,N-dioctadecylureido, N,N-dioctyl-Nxe2x80x2-ethylureido, N-phenylureido, N,N-diphenylureido, N-phenyl-N-p-tolylureido, N-(m-hexadecylphenyl)ureido, N,N-(2,5-di-t-pentylphenyl)-Nxe2x80x2-ethylureido, and t-butylcarbonamido; sulfonamido, such as methylsulfonamido, benzenesulfonamido, p-tolylsulfonamido, p-dodecylbenzenesulfonamido, N-methyltetradecylsulfonamido, N,N-dipropylsulfamoylamino, and hexadecylsulfonamido; sulfamoyl, such as N-methylsulfamoyl, N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-hexadecylsulfamoyl, N,N-dimethylsulfamoyl; N-[3-(dodecyloxy)propyl]sulfamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]sulfamoyl, N-methyl-N-tetradecylsulfamoyl, and N-dodecylsulfamoyl; carbamoyl, such as N-methylcarbamoyl, N,N-dibutylcarbamoyl, N-octadecylcarbamoyl, N-[4-(2,4-di-t-pentylphenoxy)butyl]carbamoyl, N-methyl-N-tetradecylcarbamoyl, and N,N-dioctylcarbamoyl; acyl, such as acetyl, (2,4-di-t-amylphenoxy)acetyl, phenoxycarbonyl, p-dodecyloxyphenoxycarbonyl methoxycarbonyl, butoxycarbonyl, tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 3-pentadecyloxycarbonyl, and dodecyloxycarbonyl; sulfonyl, such as methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl, 2-ethylhexyloxysulfonyl, phenoxysulfonyl, 2,4-di-t-pentylphenoxysulfonyl, methylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl, phenylsulfonyl, 4-nonylphenylsulfonyl, and p-tolylsulfonyl; sulfonyloxy, such as dodecylsulfonyloxy, and hexadecylsulfonyloxy; sulfinyl, such as methylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl, 4-nonylphenylsulfinyl, andp-tolylsulfinyl; thio, such as ethylthio, octylthio, benzylthio, tetradecylthio, 2-(2,4-di-t-pentylphenoxy)ethylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, and p-tolylthio; acyloxy, such as acetyloxy, benzoyloxy, octadecanoyloxy, p-dodecylamidobenzoyloxy, N-phenylcarbamoyloxy, N-ethylcarbamoyloxy, and cyclohexylcarbonyloxy; amine, such as phenylanilino, 2-chloroanilino, diethylamine, dodecylamine; imino, such as 1 (N-phenylimido)ethyl, N-succinimido or 3-benzylhydantoinyl; phosphate, such as dimethylphosphate and ethylbutylphosphate; phosphite, such as diethyl and dihexylphosphite; a heterocyclic group, a heterocyclic oxy group or a heterocyclic thio group, each of which may be substituted and which contain a 3 to 7 membered heterocyclic ring composed of carbon atoms and at least one hetero atom selected from the group consisting of oxygen, nitrogen and sulfur, such as 2-furyl, 2-thienyl, 2-benzimidazolyloxy or 2-benzothiazolyl; quaternary ammonium, such as triethylammonium; and silyloxy, such as trimethylsilyloxy.
If desired, the substituents may themselves be further substituted one or more times with the described substituent groups. The particular substituents used may be selected by those skilled in the art to attain the desired desirable properties for a specific application and can include, for example, hydrophobic groups, solubilizing groups, blocking groups, and releasing or releasable groups. When a molecule may have two or more substituents, the substituents may be joined together to form a ring such as a fused ring unless otherwise provided.